Fuel cell, fuel cell power source system and electronic devices using the same
Provided is a fuel cell having a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for allowing fuel to pass therethrough to the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the lo outside of the cathode electrode, an anode current collector and anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and a cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer. The anode endplate or anode current collecting layer is hydrophilic or the end plate on the anode side has a constitution promoting discharge of a gas generated by the reaction.
This application claims priority from Japanese application serial No. 2005-230587, filed on Aug. 9, 2005, the content of which is hereby incorporated into this application.
FIELD OF THE INVENTIONThe present invention relates to a fuel cell power source system composed of an anode, an electrolyte membrane, a cathode and a diffusion layer and carries out oxidation of fuel at the anode and reduction of oxygen at the cathode, particularly to a small-sized mobile fuel cell power source system using liquid fuel such as methanol, dimethyl ether or ethylene glycol and mobile electric or electronic devices using the system.
BACKGROUND OF THE INVENTIONWith the recent development of electronic technologies, cellular phones, laptop personal computers, digital cameras, audio-visual equipment, personal digital assistants and the like have become compact, and have spread widely as mobile electronic devices. Such mobile electronic devices are conventionally driven by a secondary battery. The successive appearance of new secondary batteries, that is, a seal lead battery, Ni/Cd battery, Ni/hydrogen battery and Li ion battery in the order of mention and technologies for size/weight reduction and attaining high energy density have supported the development of them. In any of these secondary batteries, a battery activating substance and a battery structure permitting a high capacity have been developed in order to heighten the energy density. Efforts have been made to prolong the serviceable time of the secondary battery per charging. These secondary batteries however have to be charged after consumption of a predetermined volume of power, and they therefore require charging equipment and a relatively long charging time. Thus, many problems have still remained in continuous operation of mobile electronic devices for long hours. Mobile electronic devices tend to require a power source having a higher output power density and a higher energy density to meet an increasing information amount and increasing processing speed in future. There is therefore an increasing demand for a small-sized power generator (micro power generator) which does not need charging.
A fuel cell power source system is considered as a system capable of meeting such a demand. A fuel cell directly converts chemical energy of fuel to electrical energy through electrochemical reaction. Accordingly, there is a high possibility of this system being realized as a small-sized power generating device, because it does not need a power output portion such as power generator using an internal combustion engine such as ordinarily employed engine power generator. In addition, a fuel cell enables continuous power generation only by replacing fuel or refilling fuel. It is not necessary to interrupt the operation of a mobile electronic device when its battery such as a secondary battery is charged. Under such a demand, a polymer electrolyte fuel cell (PEFC) using a perfluorocarbon sulfonic acid resin electrolyte membrane and carrying out oxidation of a hydrogen gas at an anode and reduction of oxygen at a cathode is under development. When it is used as a power source of a mobile electronic device, the volume of a fuel tank must be increased because of a low volumetric energy density of a hydrogen gas as fuel. This cell is therefore unsuited for size reduction.
Compared with a gas, liquid fuel is advantageous as fuel for fuel cell of small-sized devices because its density is higher than that of a gas. A fuel cell using liquid fuel such as methanol, ethanol, propanol, dimethyl ether or ethylene glycol is considered promising as a power source for small-sized devices which can be operated for long hours.
By using a direct methanol fuel cell (which will hereinafter be abbreviated as “DMFC”) which is a standard one as an example of a fuel cell power source using liquid fuel, the principle of a DMFC power source will next be described. The DMFC is composed of a cell, a fuel container, a fuel supply apparatus and air or an air supply apparatus. The cell is obtained by connecting, in series or if necessary in parallel to each other, unit cells having a porous anode electrode and a cathode electrode on respective sides of a solid electrolyte, an anode diffusion layer and a cathode diffusion layer disposed outside of these electrodes, and an anode endplate and a cathode endplate disposed on the outside of the anode diffusion layer and cathode diffusion layer, respectively and having a current collecting function. When methanol is used as fuel, methanol passing through the anode diffusion layer and coming in contact with the catalyst at the anode electrode reacts with water in accordance with the reaction formula (1) and dissociates into carbon dioxide, hydrogen ions and electrons.
CH3OH+H2O→CO2+6H++6e− (1)
The hydrogen ions reach the cathode electrode, passing through an electrolyte in the anode electrode and a solid electrolyte membrane between the anode electrode and cathode electrode. Oxygen fed to the cathode electrode and electrons entering from the outside circuit are brought into contact with a cathode catalyst, whereby reaction occurs in accordance with the following reaction formula (2) to generate water.
6H++3/2O2+6e−3H2O (2)
Electrons emitted from methanol pass through a catalyst carrier in the anode electrode and the anode diffusion layer, collected in the anode current collector and introduced into the outside circuit. From the outside circuit, they flow into the cathode electrode, passing through the cathode current collector and cathode diffusion layer. As a result, electrons move from the anode electrode toward the cathode electrode in the outside circuit, leading to power generation.
In the total chemical reaction occurring upon power generation, methanol is oxidized by oxygen and produces a carbon dioxide gas and water as shown below in the reaction formula (3). Its reaction formula is therefore formally similar to that of flaming combustion of methanol. In a fuel cell using an aqueous methanol solution as fuel, power generation occurs as direct conversion of chemical energy of methanol to electrical energy in the above-described electrochemical reaction.
CH3OH+3/2O2→CO2+3H2O (3)
In the conventional DMFC, carbon dioxide generated in the reaction formula (1) and carbon monoxide which is an intermediate product accumulate in the anode electrode, anode diffusion layer or anode endplate and disturb the supply of fuel, which deteriorates a power generation efficiency, decreases an effective surface area of a catalyst to reduce an output voltage, and increases an internal pressure to disturb supply of fuel, resulting in a reduction in the output voltage. Smooth discharge of a gas adsorbed as a foam to the electrode surface, diffusion layer or anode endplate to prevent an increase in the internal pressure is therefore indispensable for stable supply of fuel and attaining a predetermined output voltage. In particular, in a passive type DMFC not using a forced mechanism such as pump for fuel supply, smooth discharge of a gas such as carbon dioxide generated at an anode and prevention of an increase in internal pressure are necessary and indispensable.
There have been proposed methods of releasing a gas such as carbon dioxide remaining at an anode electrode, for example, by adding a defoaming agent to an aqueous methanol solution, incorporating a defoaming agent in an electrode, or, as described in Japanese Patent Unexamined Publication No. 2004-039307, incorporating a trapping agent of carbonate ions in an anode electrode or fuel supply portion. In the method of adding a defoaming agent to an aqueous methanol solution, however, the amount of the defoaming agent increases owing to accumulation of it with the passage of time, which poisons an anode catalyst, thereby deteriorating the catalyst capacity of the anode electrode. In the method of incorporating a defoaming agent in an electrode, the defoaming agent poisons an anode catalyst and lowers the catalyst capacity, which leads to drawbacks such as increase in the internal pressure and reduction in the fuel supply capacity. Another method proposed is to release carbon dioxide remaining at an anode electrode by oscillation or forced circulation of fuel by a pump. Such a method is not satisfactory when the recent tendency to size/weight reduction is considered, because it consumes power for oscillation or fuel circulation.
There is accordingly an eager demand for the establishment of a method for releasing a carbon dioxide gas which method is effective for long hours, in order to prevent an increase in internal pressure or reduction in the fuel supply capacity which will otherwise occur by a gas adsorbed as a foam to the anode diffusion layer or anode endplate.
An object of the present invention is, in order to prevent an output reduction of a fuel cell which will otherwise occur owing to the disturbance of fuel supply by the accumulation, in an anode diffusion layer or anode endplate, of a gas such as carbon dioxide produced by the reaction between methanol and water at an anode electrode or carbon monoxide which is an intermediate product of the carbon dioxide, to smoothly discharge the gas adsorbed in the form of foam to the anode diffusion layer or anode endplate.
SUMMARY OF THE INVENTIONIn the present invention, there is thus provided a fuel cell which comprises a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for causing penetration therethrough of the fuel to the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water produced and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector and anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer, wherein at least the anode endplate or anode diffusion layer is hydrophilic or anode endplate has a structure promoting discharge of a gas generated by reaction.
According to the present invention, a carbon dioxide gas generated by the reaction of a cell is discharged efficiently so that output of the cell can be maintained for long hours without lowering it.
BRIEF DESCRIPTION OF THE DRAWINGS
The present inventors investigated a method of preventing the adsorption of a gas such as carbon dioxide or carbon monoxide generated at an anode to an anode diffusion layer or endplate in details and as a result, they completed the present invention. The present invention makes it possible to provide a fuel cell capable of preventing adsorption of a gas such as carbon dioxide or carbon monoxide generated at an anode to an anode diffusion layer or anode endplate, supplying a fuel promptly and achieving a high output stably; and a manufacturing method of the fuel cell.
A first method to attain the above-described object is to maintain a hydrophilic property of a material of the anode diffusion layer, which is ordinarily subjected to water repellent treatment, in order to discharge a gas from the anode diffusion layer promptly, prevent an increase in an internal pressure and obtain a high output stably for a prolonged period of time.
The term “has a hydrophilic property” as used herein means that the material has a contact angle with water not greater than 700. Contact angles not greater than 500 are highly effective, with contact angles not greater than 200 being more preferred. At contact angles less than 200 meaning ultra-high hydrophilic property, the material exhibits the best performance.
A second method is to subject the anode diffusion layer to hydrophilization treatment in order to discharge a gas from the anode diffusion layer promptly, prevent an increase in an internal pressure and obtain a high output stably for a prolonged period of time.
A third method is to adjust a short side/long side ratio of each slit of the anode endplate and current collector, which is illustrated in
A fourth method is to incline the anode endplate and current collector so that the slit width thereof is widened from the anode diffusion layer side toward the fuel chamber side in order to discharge a gas from the anode diffusion layer promptly, prevent an increase in an internal pressure and obtain a high output stably for a prolonged period of time.
A fifth method is to roughen the surface of the anode endplate physically using sandblast or the like in order to discharge a gas from the anode diffusion layer promptly, prevent an increase in an internal pressure and obtain a high output stably for a prolonged period of time.
A sixth method is to hydrophilize the anode endplate in order to discharge a gas from the anode diffusion layer promptly, prevent an increase in an internal pressure and obtain a high output stably for a prolonged period of time. Use of some of the first to sixth methods in combination is more preferred.
Based on them, preferred embodiments of the present invention will next be described. A first embodiment is a fuel cell which comprises a membrane electrode assembly for generating power by oxidizing methanol fuel at an anode electrode and reducing oxygen in the air at a cathode electrode, an anode diffusion layer which is placed on a side opposite to the cathode electrode of the membrane electrode assembly, causes the fuel to pass through the diffusion layer and transfers electrons generated by the oxidation, a cathode diffusion layer for removing water produced and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector which is brought into contact with the anode diffusion layer directly or via another member and transfers electrons generated by the oxidation, an anode endplate brought into electrical contact with the anode current collector, a cathode current collector which is brought into contact with the cathode diffusion layer directly or via another member and transfers electrons to be used for the reduction, and a cathode endplate brought into electrical contact with the cathode current collector, wherein the anode endplate is hydrophilic and the fuel cell has a structure permitting contact with the air on the side of the cathode current collector. This fuel cell is a passive type and does not need any auxiliary apparatus for air circulation or fuel circulation.
A second embodiment is a fuel cell which comprises a membrane electrode assembly having an electrolyte membrane and electrode, a cathode diffusion layer and anode diffusion layer disposed on the respective sides of the membrane electrode assembly, a cathode current collector and anode current collector disposed outside of the diffusion layers, and end-plates encompassing therewith the cathode current collector and anode current collector and having slits; wherein the cathode diffusion layer is brought into contact with air through the slits on the side of the cathode current collector, methanol fuel is brought into contact with the anode diffusion layer through the slits on the side of the anode current collector, and a region of the anode endplate encompassing therewith the anode current collector, which endplate is brought into contact with the methanol fuel, is hydrophilic. This fuel cell is also a passive type.
In the embodiment of the present invention, (1) either or both of the cathode endplate and anode diffusion layer may be hydrophilized. Moreover, it embraces (2) a fuel cell wherein the slits of the anode current collector each has a short side/long side ratio of from 0.5 to 0.92 and (3) a fuel cell wherein the anode current collector is inclined so that the slits become wider from the electrode side toward the fuel chamber side. These (1) to (3) may be used either singly or in combination with another method.
The embodiments of the present invention will hereinafter be described more specifically. When any of the embodiments of the present invention is applied to a fuel cell, an increase in an internal pressure can be prevented, fuel can be supplied smoothly and output of a fuel cell can be stabilized by preventing adsorption of a gas such as carbon dioxide or carbon monoxide generated at an anode to an anode diffusion layer or anode endplate or removing the gas adsorbed thereto in the form of foam.
As the cathode diffusion layer and anode diffusion layer, a water-repellent carbon cloth or carbon paper is conventionally used. In the first embodiment of the present invention, a water repellent function conventionally given to the anode diffusion layer is removed therefrom. This facilitates separation of a gas such as carbon dioxide or carbon monoxide from the anode diffusion layer, prevents an increase in the internal pressure which will otherwise occur by the gas, enables prompt fuel supply, and stabilizes the output of a fuel cell. For elimination of the water repellent function from the anode diffusion layer, a carbon cloth or carbon paper not subjected to water repellent lo treatment is used as the anode diffusion layer instead of the conventional water-repellent carbon cloth or carbon paper. Examples of the carbon cloth or carbon paper not subjected to water repellent treatment include “Carbon Paper TGP-H-030, TGP-H-060, TGP-H-090 and TGP-H-120” (each, trade name; product of Toray) and carbon cloth manufactured by Mitsubishi Rayon. Use of a diffusion layer obtained by exposing a water repellent carbon cloth or carbon paper to oxygen plasma to remove therefrom the water repellent is also effective. Single use of the first embodiment is insufficient and use of it with any of the second to sixth embodiments in combination is preferred.
In the second embodiment, the anode diffusion layer is hydrophilized. No particular limitation is imposed on the hydrophilization method insofar as it can impart the anode diffusion layer with a hydrophilic property. Examples of the recommendable method include (1) treatment of the anode diffusion layer with an oxidizing agent selected from hydrogen peroxide, sodium hypochlorite, potassium permanganate, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, acetic acid and ozone to introduce a hydrophilic group such as hydroxyl, sulfonic acid, carboxyl, phosphoric acid, sulfate ester, carbonyl or amino group into carbon, (2) activating treatment such as electrolytic oxidation (anodization) and steam oxidation and (3) addition of a hydrophilization agent.
Specific methods of them include (1) addition of a hydroxyl group or carbonyl group by treating carbon paper or carbon cloth used as the anode diffusion layer with oxygen plasma, addition of a sulfonic acid group or hydroxyl group to the surface of carbon of carbon paper or carbon cloth used as the anode diffusion layer by treating it with fuming sulfuric acid, and addition of sulfonic acid group to the surface of carbon of carbon paper or carbon cloth used as the anode diffusion layer by sulfonation treatment, (2) activation treatment of carbon paper or carbon cloth used as the anode diffusion layer by positive vapor oxidation, and (3) treatment of carbon paper or carbon cloth used as the anode diffusion layer with a hydrophilizing agent and treatment of carbon paper or carbon cloth used as the anode diffusion layer with a hydrophilic surfactant.
In the third embodiment, the CO2 release holes of the anode endplate are inclined to widen them from the side of the anode diffusion layer toward the side of the fuel chamber. No particular limitation is imposed on the inclination angle insofar as a gas such as carbon dioxide or carbon monoxide is not trapped by the anode endplate.
In the third embodiment, an opening ratio of the anode endplate is adjusted to from 30 to 60%, preferably from 35 to 45%. At lower opening ratios, a gas such as carbon dioxide or carbon monoxide cannot be removed easily and fuel supply tends to become unstable. Higher opening ratios, on the other hand, decrease the area of a collector plate, increase electrical resistance and tend to cause a reduction in output.
In the fourth embodiment, the surface of the anode endplate is roughened physically, more specifically, roughened by polishing with sandblast or sand paper.
In the fifth embodiment, the anode endplate is hydrophilized. No particular limitation is imposed on the hydrophilization method insofar as it can decrease the contact angle with water to 500 or less, preferably 40° or less. Examples of the hydrophilization method of the anode endplate include (1) exposure to electron beams, (2) exposure to oxygen plasma, (3) corona discharge treatment, (4) ozone UV treatment (5) addition of a sulfurous acid gas or sulfuric acid to introduce a sulfonic acid group, and (6) treatment with a hydrophilizing agent. Hydrophilization treatment by (1) exposure to electron beams, (2) exposure to oxygen plasma, (3) corona discharge treatment or (4) ozone UV treatment is very effective just after treatment because the anode end plate does not trap a gas such carbon dioxide or carbon monoxide, but when the anode end plate is incorporated in a fuel cell, its effect gradually decreases during use.
In particular, (6) treatment with a hydrophilizing agent is effective. It is preferred to improve the wetness of the surface of the anode endplate in advance by exposing it to UV rays or oxygen plasma to the anode endplate, or allowing it to stand in an oxygen plasma atmosphere or ozone atmosphere prior to the treatment with a hydrophilizing agent. A high pressure mercury lamp or ultra high pressure mercury lamp can be used for exposing it to UV rays, but a lamp such as deep UV lamp or low pressure mercury lamp which can easily produces ozone by emitting a UV light at 254 nm or 185 nm is effective. When the anode plate is flat, exposure to UV light or oxygen plasma is effective, while when the anode plate has a surface with many irregularities, it is preferably allowed to stand in an oxygen plasma or ozone atmosphere. In the above-described treatment, when the anode endplate is made of an acrylic resin, hydrophilization conditions must be set so that the contact angle with water be 50° or less after the treatment, showing a decrease from that of about 95° before the treatment.
When the anode endplate is made of polycarbonate or PMMA, the conditions are also set to decrease the contact angle after the treatment to 50 degree or less. When it is made of a hydrocarbon resin such as polyethylene or polypropylene, the conditions must be set severer compared with the case of the acrylic resin to decrease the contact angle with water, which is from about 80 to 90 before treatment, to 50 degree or less after the treatment. By heating the anode endplate during exposure to UV rays, the hardness of a hydrophilic film formed by the application of a hydrophilic coating and heat curing can be improved drastically.
The heating temperature may be set near the thermal deformation temperature (specifically, thermal deformation temperature ±20° C.) of the anode endplate. For example, when the anode endplate has a thermal deformation temperature of 100° C., the heating temperature is set at from 80 to 120° C. When it has a thermal deformation temperature of 110° C., the heating temperature is set at from 90 to 130° C. By the hydrophilization as described above, a hydrophilic film, which has only a pencil harness of 2B or less when not subjected to hydropohilization, can have a pencil hardness of several H. The term “thermal deformation temperature” as used herein is defined as “temperature at which warpage of a plate having a predetermine size (height×width×thickness=100 mm×100 mm×5 mm) occurs by heating. The heating time is for 30 minutes. Even if the heating temperature is higher than the thermal deformation temperature, such a short heating time enables hydrophilization without causing deformation.
A hydrophilic coating is then applied. Ordinarily employed application methods such as dip coating, spin coating, spray coating and bar coating can be employed for it.
Heating is then conducted. The heating temperature must be set at a temperature lower than the thermal deformation temperature of the anode endplate. During curing, the film surface is heated smoothly at a curing temperature which facilitates the formation of pores in the hydrophilic film.
(2) Hydrophilic Coating
The hydrophilic coating is composed of a hydrophilic material, a support material for supporting the hydrophilic material therewith, and a solvent.
(a) Hydrophilic Material
Examples of the hydrophilic material include organic polymer materials such as polyethylene glycol and polyvinyl alcohol, and inorganic materials such as hydrophilic alumina particles and hydrophilic silica particles. Of these, inorganic materials such as hydrophilic alumina particles and hydrophilic silica particles are excellent because they can keep hydrophilicity long without causing elution even immersed in water for a long period of time (these inorganic materials become corresponding inorganic oxides). These inorganic fine particles often exist as a water dispersion and in this case, the coating containing them has an increased water content. When the coating is applied to the surface of a base material and dried, an increased water content leads to the possibility of the coating being repelled on the surface of the base material. This owes to a surface tension of water, 72 mN/m, greater than that of an ordinarily employed organic solvent. As the solvent for dispersing the hydrophilic material therein, that having a surface tension of from 20 to 30 mN/m and smaller than that of water, for example alcohol orethyl methyl ketone, is excellent from the viewpoint of a film forming property. As the hydrophilic material to be used in the present invention, hydrophilic silica particles are especially preferred, because they can be dispersed in an organic solvent such as alcohol or ethyl methyl ketone. Specific examples include “Colloidal silica IPA-ST” and “MEK-ST” (trade name) each product of Nissan Chemical.
(b) Support Material
Examples of the support material include organic polymer materials such as polyethylene glycol and polyvinyl alcohol, organic materials such as polyacrylamide which are polymerized into a support material by heating, and materials such as silica sol which become an inorganic support material by heating. Of these, materials such as acrylamide and silica sol are superior because they are free from elution even immersed in water for long hours and therefore, they can maintain a hydrophilic property for a long period of time. When the suitability with the hydrophilic material which is supported by the support material is taken into consideration, silica sol is especially suited for inorganic materials.
The term “silica sol” means that obtained by heating an alkoxysilane in water acidified with dilute hydrochloric acid, dilute nitric acid or dilute phosphoric acid or a water-alcohol mixture to cause self-polymerization and having a molecular weight of several thousands. Examples of the alkoxysilane include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane. Instead of an alkoxysilane, an alkoxytitanium may be used if its liquid property or solvent does not disturb the preparation of the above-described silica sol. Examples of the alkoxytitanium include tetra-i-propyl titanate, tetra-n-butyl titanate, tetrastearyl titanate, triethanolamine titanate, titanium acetyl acetonate, titanium ethylacetoacetate, titanium lactate, and tetraoctylene glycol titanate. Compounds obtained by polymerizing several molecules of the exemplified compound can also be used.
Even use of an amino-containing alkoxysilane instead of the above-described silica sol can also attain a similar supporting performance to that of the silica sol. In addition, when the amino-containing alkoxysilane is exposed to an acidic gas atmosphere, the amino group is converted into an ammonium salt structure, resulting in a further improvement in the hydrophilic property of the film. Examples of such a material include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (for example “Sila-Ace S310”, trade name; product of Chisso Corporation), 3-aminopropyltriethoxysilane (“Sila-Ace S330”, trade name; product of Chisso Corporation), and 3-aminopropyltrimethoxysilane (“Sila-Ace S360”, trade name; product of Chisso Corporation). “Sila-Ace Oligomer MS3201” or MS3301” (each, trade name; product of Chisso Corporation) which are compounds obtained by polymerizing several molecules of “S320” or “S330” can also be employed.
(c) Solvent
Solvents having good suitability (dispersibility, compatibility) with the hydrophilic material or support material and vaporizing easily during heat curing are preferred. In order to form voids in the hydrophilic film, solvents preferably have a boiling point lower than the heat curing temperature. Alcohol solvents are preferred because they can effectively disperse therein hydrophilic alumina particles or hydrophilic silica particles which are desirable materials having high durability. Alcohol solvents are also preferred because they have high compatibility with silica sol which is preferred as the support material. The acrylic resin and polycarbonate resin have a heat curing temperature of 100° C. or less and 120° C. or less, respectively so that when the heat resistance of the resin is taken into consideration, alcohol solvents usable for them are, for example, methanol, ethanol, n-propanol and isopropanol have a boiling point of 100° C. or less. Use of a solvent such as n-butanol having a higher boiling point than that of n-propanol causes an excessive increase in a porosity, which tends to lower the hardness. In order to adjust the pencil hardness of a hydrophilic film to 2H or greater, a porosity is preferably adjusted to fall within a range of from 2 to 14% by volume of the hydrophilic film.
(d) Lubricating Material
There is a method of improving the surface lubrication, thereby improving friction resistance. Addition of a silicone lubricating material in an amount of from 0.01 to 0.5 wt. % based on the solid content improves the lubrication, thereby improving the friction resistance. Amounts of 2% or greater based on the solid content however tend to deteriorate the hydrophilic property on the surface. A silicone lubricating material is preferably soluble in a solvent of a coating used for the formation of a hydrophilic film, but a lubricating material which is insoluble but can be dispersed almost uniformly for a predetermined time by stirring can also be used. Specific examples include “BYK-370” and “BYK-310” (each trade name; product of BYK-Chemie).
The membrane electrode assembly (MEA) to be used in the present invention will next be described. No particular limitation is imposed on a solid polymer electrolyte membrane used for MEA insofar as it has proton conductivity. Specific examples include fluorine series solid polymer electrolyte membranes typified by a polyperfluorosulfonic acid membrane which is known under the commodity name of “Nafion” (trade mark, product of Dupont), “Aciplex” (trademark; product of Asahi Kasei Kogyo) or “Flemion” (trade mark;,product of Asahi Glass); partially fluorinated solid polymer electrolyte membranes such as sulfonic acid polystyrene-graft-ethylenetetrafluoroethylene copolymer (ETFE) membrane composed of a main chain prepared by the copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer and a hydrocarbon side chain having a sulfonic acid group, and a sulfonic acid type poly(trifluorostyrene)-graft-ETFE membrane obtained as a solid polymer electrolyte membrane by carrying out graft polymerization of a,β,β-trifluorostyrene to a membrane prepared by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer and then introducing a sulfonic acid group into the resulting graft polymer; sulfonated engineering plastics electrolyte membranes such as sulfonated polyetheretherketone, sulfonated polyethersulfone, sulfonated acrylonitrile-butadiene-styrene polymer, sulfonated polysulfide and sulfonated polyphenylene; sulfolalkylated engineering plastics electrolyte membranes such as sulfoalkylated polyetheretherketone, sulfoalkylated polyethersulfone, sulfoalkylated polyetherethersulfone, sulfoalkylated polysulfone, sulfoalkylated polysulfide, sulfoalkylated polyphenylene, and sulfoalkylated polyetherethersulfone; and aromatic hydrocarbon solid polymer electrolyte membranes such as sulfoalkyletherified polyphenylene. Of these, aromatic hydrocarbon solid polymer electrolyte membranes are preferred from the viewpoint of methanol permeability. Especially, aromatic hydrocarbon solid polymer electrolyte membranes having an alkylenesulfonic acid group introduced therein are preferred from the viewpoints of methanol permeability, swelling property and durability.
Fuel cells which can be operated even in a higher-temperature region can be obtained by using a composite electrolyte membrane obtained by the micro-dispersion, in a heat resistant resin, of a proton conductive inorganic material such as tungsten oxide hydrate, zirconium oxide hydrate, tin oxide hydrate, silicotungstic acid, silicomolybdic acid, tungstophosphoric acid or molybdophosphoric acid. In the above-described acid electrolyte membrane in the form of a hydrate, owing to a difference in a swelling rate between drying time and wet time, the membrane changes its shape so that a membrane having a sufficient ion conductivity sometimes has insufficient mechanical strength. In such a case, fibers excellent in mechanical strength, durability and heat resistance are used in the form of a woven or nonwoven fabric as a core material and during preparation of an electrolyte membrane, these fibers are added as a filler to reinforce the membrane. This method is effective for heightening the reliability of the performance of a fuel cell. Also a membrane obtained by doping sulfuric acid, phosphoric acid, sulfonic acid or phosphonic acid into a polybenzimidazole in order to reduce the fuel permeability of an electrolyte membrane can be used.
The sulfonic acid equivalent of such a solid polymer electrolyte membrane is preferably from approximately 0.5 to 2.0 milliequivalent/g dry resin, more preferably from 0.7 to 1.6 milliequivalent/g dry resin. The sulfonic acid equivalent below the above-described range increases the ion conductivity resistance of the membrane, while that exceeding the above-described range results in high water-solubility. The sulfonic acid equivalents outside the above-described range are therefore not preferred.
Although no particular limitation is imposed on the thickness of the solid polymer electrolyte membrane, it is preferably from 10 to 200 μm, especially preferably from 30 to 100 μm. Thickness greater than 10 μm is preferred in order to impart the membrane with strength enough to endure the practical use, while thickness smaller than 200 μm is preferred in order to reduce the resistance of the membrane, that is, improve the power generation performance. When a solution casting method is employed, the film thickness can be controlled by the concentration of the solution or application thickness onto a substrate. When a membrane is formed from a molten state, the film thickness can be controlled by extending, at a predetermined ratio, a film having a predetermined thickness obtained by melt press or melt extrusion method.
When a solid polymer electrolyte membrane to be used in the present invention is prepared, an additive such as plasticizer, stabilizer or mold release agent which is ordinarily used for polymers may be added within a range not contrary to the object of the present invention.
An electrode to be used for the membrane electrode assembly (MEA) for a fuel cell is composed of a conductive material having fine particles of a catalyst metal supported thereon and it may contain a water repellent or binder as needed. Further, a layer composed of a conductive material having no catalyst supported thereon and a water repellant or a binder contained as needed may be formed outside of the catalyst layer. As the catalyst metal used for the electrode, any metal capable of promoting the oxidation reaction of hydrogen and the reductive reaction of oxygen can be used. Examples include platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, nickel, chromium, tungsten, manganese and vanadium, and alloys thereof.
Of these catalysts, platinum is used frequently. A particle size of the metal serving as a catalyst is usually from 10 to 300 Angstroms. It is advantageous to attach these catalysts to a carrier such as carbon, because it decreases their using amount and reduces a cost. The amount of the catalyst supported by a carrier after formation of the electrode is preferably from 0.01 to 10 mg/cm2. No particular limitation is imposed on the thickness of the catalyst layer, it is preferably from 10 to 100 μm, especially preferably from 10 to 50 μm. The thickness is preferably 10 μm or greater in consideration of the durability, while it is preferably 50 μm or less in consideration of the efficiency of the catalyst. The anode catalyst layer is preferably thicker than the cathode catalyst layer because the reaction of an aqueous solution of fuel such as methanol in the chemical formula (I) is slow. The thickness of the anode catalyst layer is preferably from 10 to 200 μm, especially preferably from 50 to 150 μm. The thickness of the cathode catalyst layer is preferably from 1 to 50 μm, especially preferably from 5 to 20 μm. The anode catalyst layer and anode diffusion layer are preferably hydrophilized in order to improve wetness with the aqueous solution of fuel such as methanol. On the contrary, the cathode diffusion layer is preferably subjected to water repellent treatment in order to prevent retention of produced water.
As the conductive material having the catalyst supported thereon, any electron conductive material can be used. Examples include various metals and carbon materials. Examples of the carbon materials include furnace black, channel black, acetylene black, amorphous carbon, carbon nanotube, carbon nanohorn, active carbon and graphite. They may be used either singly or as a mixture. The carbon particles have a particle size of, for example, 0.01 μm or greater but not greater than 0.1 μm, preferably 0.02 μm or greater but not greater than 0.06 μm. As the repellant, fluorinated carbon, polytetrafluoroethylene or the like can be used.
As the binder, it is preferred, in view of adhesion, to use an electrode catalyst covering solution as described in the embodiment of the present invention as is, but another resin may be used. In the latter case, addition of a fluorine-containing resin having water repellency is preferred, with addition of the resin further having excellent heat resistance and oxidation resistance being more preferred. Examples include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinylether copolymer, and tetrafluoroethylene-hexafluoropropyrene copolymer. The cathode electrode (carrier) is preferably subjected to water repellent treatment, while the anode electrode (carrier) is preferably subjected to no treatment or hydrophilization treatment.
No particular limitation is imposed on the process of joining an electrolyte membrane and an electrode which are used for a fuel cell and any known process can be employed. For example as a manufacturing process of MEA, a Pt catalyst powder supported by a conductive material such as carbon is mixed with a polytetrafluoroethylene suspension. The resulting mixture is applied to carbon paper, followed by heat treatment to form a catalyst layer. An electrolyte solution similar to the electrolyte membrane or a fluorine electrolyte is applied as binder to the catalyst layer, and the catalyst layer and the electrolyte membrane are hot pressed, whereby they are formed as an assembly. Additional examples of the MEA manufacturing process include a process of coating a Pt catalyst powder with an electrolyte solution similar to that of the membrane electrolyte assembly, a process of applying a catalyst paste to an electrolyte membrane by printing, spraying, slit spraying or inkjet, a process of electroless-depositing an electrode on an electrolyte membrane, a process of adsorbing platinum group metal complex ions to an electrolyte membrane, followed by reduction. Of them, a process of applying a catalyst paste to an electrolyte membrane by ink jet process does not produce much catalyst loss and is therefore excellent.
DMFC is obtained by stacking, via a cooling plate, a plurality of unit cells one after another, each having a fuel flow distribution panel and an oxidant flow distribution channel as current collectors equipped with channels for forming a fuel flow channel and an oxidant flow channel on the outside of the MEA formed as described above. The unit cells may be connected by, in addition to stacking, arranging them in parallel to each other. No particular limitation is imposed on the connecting method of the unit cells.
There is no particular limitation imposed on the fuel cell insofar as it is a direct type fuel cell using liquid fuel such as methanol, ethanol, dimethyl ether or ethylene glycol. The fuel cell can be roughly classified into two systems, a circulation system which supplies fuel to an anode by a pump and recycles the unused fuel and water by-produced at a cathode; and a passive system which supplies fuel by a cartridge or the like and supplies air at a cathode, depending on natural convection. The latter system is especially effective because the flow of the fuel is weaker than that of the circulation system.
One constitution example of such a passive power source system according to this Example is illustrated in
The battery output system supplies electric power to load equipment via a DC/DC converter 5. The power source system is equipped with a controller 6 which receives signals related to the fuel cell 1, the remaining amount of the fuel in the fuel cartridge tank 2 and the state during operation and termination of the DC/DC converter 5, controls the DC/DC converter 5 and is set to output a warning signal depending on the condition. If necessary, the controller 6 is also able to display operation conditions of the power source, such as battery voltage, output current, and battery temperature, on the load equipment, and if the remaining amount of the fuel in the fuel cartridge tank 2 becomes less than a prescribed level, or if the air diffusion amount is outside a predetermined range, the controller 6 stops supplying electric power from the DC/DC converter 5 to the load equipment and activates an audible warning signal, vocal warning, pilot lamp or character warning display.
Even during normal operation, it is also possible to receive a signal indicating the fuel level in the fuel cartridge tank 2 and display it on the load equipment.
Air serving as an oxidant is supplied by diffusion from an air diffusion slit 22 and water generated at a cathode is diffused and discharged through this slit 22. The fastening method of the cell for obtaining an integrated body is not limited to fastening by screws as disclosed in this Example, but fastening by a compressive force from a chassis in which the cell is inserted, or another method can be employed.
As illustrated in
No particular limitation is imposed on the material for the fuel chamber 12 insofar as the material is smooth to allow uniform surface pressure to be applied during mounting of MEA and is also insulated so that a plurality of cells installed thereon do not mutually short-circuit. High density vinyl chloride, high-density polyethylene, high density polypropylene, epoxy resin, polyether ether ketone, polyether sulfone, polycarbonate, or such materials reinforced with glass fiber are preferably employed. It is also possible to make the surface of such a material nonconductive by using a carbon plate, steel or nickel, an alloy material such as light-weight aluminum or magnesium, intermetallic compound typified by copper-aluminum, or a variety of stainless steels or impart it with insulating properties by the application of a resin.
The slits 22 for distributing fluid such as fuel or oxidizing gas are parallel grooves in
The fuel chamber 12 may be combined with a gas discharge module. Each vapor-liquid separation tube of the gas discharge module is fixed through a support hole 24 of the rib support plate 23 provided in the fuel chamber 12. A module substrate is connected to the exhaust gas port 4 and has a function of discharging a gas collected in the vapor-liquid separation tube outside the cell. When such a structure is adopted, the vapor-liquid separation tube can be installed at almost an equal distance from two anodes which are opposite to each other in the vicinity of the anode-on which carbon dioxide is generated. When the fuel cartridge is mounted, the fuel chamber is therefore filled with fuel under a predetermined pressure. When power generation is not conducted, fuel cannot enter into the pores until the pressure reaches a certain level, disturbed by the water repellency of the vapor-liquid separation tube. Accordingly, fuel does not leak when the pressure is less than a certain level. A carbon dioxide gas generated owing to the deaeration of a gas dissolved in fuel or starting of power generation is collected in the vapor-liquid separation tube and discharged outside the cell under the pressure of the liquid fuel. The film thickness, average pore size, pore distribution and aperture ratio of the vapor-liquid separation tube are determined based on the initial and final pressures of the fuel cartridge and the production amount of a carbon dioxide gas at the maximum output time of the cell.
Preferred examples of the material include high-density vinyl chloride, high-density polyethylene, high-density polypropylene, epoxy resin, polyether ether ketone, polyether sulfone, polycarbonate, polyimide resin, or these materials reinforced with glass fiber. It is also possible to join the substrate to the current collectors 42 by making its surface non-conductive by using an alloy material such as copper, nickel, light-weight aluminum or magnesium, or an intermetallic compound typified by copper-aluminum or various stainless steels or applying a resin to the surface to impart insulation properties.
The current collectors 42 can be fixed not only by an adhesive but also by disposing, in a portion of the countersunk portions on the substrate 81, a protrusion which is fitted in some of the slits 22c disposed in the current collector 42 or in an especially disposed fitting hole. Furthermore, the current collectors 42 and one side of the substrate 81 do not necessarily form one flat surface. When there exists a step difference at this portion, current collectors 42 can be directly bonded onto the substrate 81 without providing countersunk portions 82a and 82b. In such a case, the structure or thickness of the gasket used for sealing may be changed.
No particular limitation is imposed on the material used for the current collectors 42. Examples of the material usable for them include a carbon plate, plates made of a metal such as stainless steel, titanium, or tantalum, and composite materials of such a metallic material with another metal such as carbon steel and stainless steel, and clad materials with copper or nickel. Furthermore, in the metallic current collector, it is effective to apply a corrosion resistant rare metal such as gold or to apply a conductive carbon paint to the processed electrical contact portion of the current collector SO as to reduce the contact resistance upon installation, thereby increasing the output density and long-term performance stability of the cell.
Described specifically, carbon paper (“TGP-H-060”, trade name; product of Toray) is cut into a predetermined size, and the amount of water absorption is determined in advance. The carbon paper is immersed in a diluted polytetrafluorocarbon/water dispersion (“D-1”, trade name; product of Daikin Industries, Ltd.) so that the weight ratio after the carbon paper is baked will become 20 to 60 wt %, dried at a temperature of 120° C. for about one hour, and then baked in the air at temperatures between 270 and 360° C. for 0.5 to 1 hour. To carbon powder (“XC-72R”, trade name; product of Cabot Corporation) is added a polytetrafluorocarbon/water dispersion in an amount of from 20 to 60 wt. % based on the carbon powder, followed by kneading. The kneaded mass in the paste form was applied to one side of the above-described water-repellent carbon paper until the thickness of the coating becomes 10 to 30 μm. After drying at a temperature of 120° C. for about one hour, the coating is baked in the air at temperatures between 270 and 360° C. for 0.5 to 1 hour, whereby a cathode diffusion layer 170c is obtained. The air permeability and moisture permeability of the cathode diffusion layer 170c, that is, diffusion property of supplied oxygen and generated water, greatly depends on the amount of polytetrafluoroethylene, dispersibility, and baking temperature. Therefore, appropriate conditions are selected after due consideration of the designed performance of the fuel cell and use environment.
As a material of the anode diffusion layer 70a, a woven or nonwoven cloth made of carbon fiber which is both conductive and porous, for example, carbon cloth (“Torayca cloth”, trade name; product of Toray Industries) and carbon paper (“TGP-H-060”, trade name; product of Toray Industries) are suitable. The anode diffusion layer 70a has a function of promoting supply of an aqueous fuel solution and quick dissipation of a generated carbon dioxide gas. In order to inhibit a carbon dioxide gas generated on the anode from forming bubbles in the porous carbon substrate 71a, thereby heightening the output density of the fuel cell, a method of hydrophilizing the surface of the porous carbon substrate 71a by mild oxidation or ultraviolet exposure, a method of dispersing a hydrophilic resin in the porous carbon substrate 71a, and a method of dispersing a strongly hydrophilic substance typified by titanium oxide and having the substance supported on the substrate. The material of the anode diffusion layer 70a is not limited to the above-described material but porous materials such as substantially electrochemically inactive metal materials (such as stainless steel fiber nonwoven fabric, porous materials, porous titanium, tantalum and the like) can also be used.
One example of a DMFC for personal digital assistance will hereinafter be described.
A 0.3-mm thick titanium plate is used as a material of the current collector. After the surface which comes in contact with the electrode is washed, gold of about 0.1 μm thick is deposited on the surface.
It is desired to activate a fuel cell at high temperature in order to heighten the catalytic activity of the electrode, thereby decreasing an excessive voltage of the electrode. In particular, prompt discharge of a gas such as carbon dioxide generated on an anode to prevent an increase in the internal pressure is effective in the passive type fuel cell which does not employ a forced fuel supplying mechanism such as pump.
A small-sized-power source capable of continuing power generation for long hours can be actualized by manufacturing a plurality of single cells composed of an anode, an electrolyte membrane and a cathode, connecting these single cells in series via an electroconductive interconnector to increase voltage, operate without using an auxiliary machine for supplying fuel or oxidizing agent forcedly or without using an auxiliary machine for forced cooling of a fuel cell and using as a liquid fuel an aqueous methanol solution having a high volume energy density. This small-sized power source can be driven after incorporated as a power source, for example, in a mobile phone, laptop personal computer, or mobile video camera. It can be operated for long hours by supplying fuel, which has been prepared in advance, whenever necessary. In order to drastically decrease the frequency of fuel supply compared with the above-described case, it is effective to use the small-sized power source as a battery charger after bonding it to a charger of a mobile phone equipped with a secondary battery, a laptop personal computer or a mobile video camera and installing it to a portion of its housing case. In this case, when the mobile electronic device is used, it is taken out from its housing case and driven by a secondary battery, while when it is not used, it is housed in the case and a small-sized fuel cell power generator built in the case is connected via a charger to charge the secondary battery. In this manner, the volume of a fuel tank can be increased and frequency of fuel supply can be drastically reduced.
EXAMPLESThe present invention will hereinafter be described more specifically. It should however be borne in mind that the present invention is not limited only to the examples disclosed herein.
Contact angle, foam discharging performance, internal pressure and output voltage are each measured in the following manner.
(1) Measurement of Contact Angle
Samples subjected to predetermined treatment were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The samples were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science.
(2) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage
A DMFC having a constitution as illustrated in
(1) Synthesis of Chloromethylated Polyethersulfone
After a 500-ml four-necked round-bottom flask equipped with a stirrer, a thermometer, and a reflux condenser having a calcium chloride tube connected thereto was purged with nitrogen, 30 g of polyethersulfone (PES) and 250 ml of tetrachloroethane were charged in the flask, followed by the addition of 40 ml of chloromethyl methyl ether. A mixed solution of 1 ml of anhydrous tin chloride (IV) and 20 ml of tetrachloroethane was added dropwise. The reaction mixture was heated to 80° C. and stirred under heating for 90 minutes. The reaction mixture was charged in 1 liter of methanol to precipitate the corresponding polymer. The polymer thus precipitated was pulverized in a mixer and washed with methanol to yield chloromethylated polyethersulfone. The nuclear magnetic resonance spectrum of it revealed that the introduction ratio of a chloromethyl group {a ratio of a structural unit having a chloromethyl group introduced in it relative to the whole structural unit (total of x and y) in the formula (1)} was 36%.
(2) Synthesis of Acetylthio-Introduced Polyethersulfone
The chloromethylated polyethersulfone thus obtained was charged in a 1000-ml four-necked round-bottom flask equipped with a stirrer, a thermometer, and a reflux condenser having a calcium chloride tube connected thereto. After addition of 600 ml of N-methylpyrrolidone, a solution of 9 g of potassium thioacetate and 50 ml of N-methylpyrrolidone (NMP) were added to the resulting mixture, followed by heating to 80° C. and stirring under heat for 3 hours. The reaction mixture was charged in 1 liter of water to precipitate the corresponding polymer. The precipitate thus obtained was pulverized in a mixer, washed with water, and dried by heating to yield 32 g of acetylthio-introduced polyethersulfone.
(3) Synthesis of Sulfomethylated Polyethersulfone
In a 500-ml four-necked round bottom flask equipped with a stirrer, a thermometer and a ref lux condenser having a calcium chloride tube connected thereto was charged 20 g of the resulting acetylthio-introduced polyethersulfone. To the resulting flask was added 300 ml of acetic acid. Then, 20 ml of hydrogen peroxide was added and the resulting mixture was heated to 45° C. and stirred under heat for 4 hours. The reaction mixture was then added to 1 liter of a 6N aqueous solution of sodium hydroxide while cooling and stirring was continued for a while. A polymer was obtained by filtering the reaction mixture and washed until removal of an alkaline component. The resulting polymer was added to 300 ml of 1N hydrochloric acid and the mixture was stirred for a while. The resulting mixture was filtered to yield a polymer and the polymer was washed until the removal of an acid component. The residue was dried under reduced pressure to yield 20 g of sulfomethylated polyethersulfone at a stoichiometric ratio. Existence of a sulfomethyl group was confirmed from the fact that the methylene proton of NMR showed the chemical shift to 3.78 ppm. The introduction ratio of a sulfomethyl group {a ratio of a structural unit having a sulfomethyl group introduced therein relative to the whole structural unit (total of x and y) in the formula (2)} was 36% based on the introduction ratio of a chloromethyl group.
(4) Preparation of Electrolyte Membrane
The sulfomethylated polyethersulfone obtained above in (3) was dissolved in a 1/1 mixed solvent of dimethylacetamide and methoxyethanol so as to give a 5 wt. % concentration. The resulting solution was applied onto glass by spin coating, air-dried and vacuum dried at 80° C. to prepare a sulfomethylated polyethersulfone electrolyte membrane of 42 μm thick. The methanol permeability and ion conductivity of the resulting electrolyte membrane at room temperature were 12 mA/cm2 and 0.053 S/cm, respectively.
(4) Preparation of Electrolyte Membrane Electrode Assembly (MEA)
A slurry of a catalyst powder having 50 wt. % of 1/1 (atomic ratio)-platinum/ruthenium alloy fine particles dispersed and borne on a carbon carrier and a 30 wt. % solution of the sulfomethylated polyethersulfone in a mixed solvent of 1-propanol, 2-propanol and methoxyethanol was prepared and an anode porous membrane of about 30 μm thick was formed over a polyimide film by screen printing. Then, a slurry in a water/alcohol mixed solvent was prepared using a catalyst powder having 30 wt. % of platinum fine particles borne on a carbon carrier and a solution of the sulfomethylated polyethersulfone obtained above in (3) in 1-propanol, 2-propanol and methoxyethanol as a binder. By using the resulting slurry, a cathode porous membrane of about 10 μm thick was formed on a polyimide film by screen printing. The anode porous membrane and cathode porous membrane thus prepared were cut respectively into anode electrode and cathode electrode of 10 mm wide and 20 mm long.
After the surface of the anode electrode was immersed with about 0.5 ml of a 5 wt. % solution of the sulfomethylated polyethersulfone obtained above in (3) in a mixed solvent of 1-propanol, 2-propanol and methoxyethanol, the resulting anode electrode was bonded to a power generation portion of the sulfomethylated polyethersulfone electrolyte membrane obtained above in (4) and cut into a 16 mm×33 mm piece. A load of about 1 kg was applied and dried at 80° C. for 3 hours. The surface of the cathode electrode was then immersed with about 0.5 ml of a 5 wt. % solution of the sulfomethylated polyethersulfone in a mixed solvent of 1-propanol, 2-propanol and methoxy ethanol. The resulting cathode electrode was bonded to the electrolyte membrane so that it overlapped the anode layer bonded previously. About 1 kg of a load was applied to the cathode electrode, followed by drying at 80° C. for 3 hours to yield an MEA (i).
A slurry of a catalyst powder having 50 wt. % of a 1/1 (atomic ratio) platinum/ruthenium alloy fine particles dispersed and borne on a carbon catalyst and a 30 wt. % of a solution of the sulfomethylated polyethersulfone obtained above in (3) in a mixed solvent of 1-propanol, 2-propanol and methoxyethanol was prepared. By using the resulting slurry, an anode porous membrane of about 30 μm thick was formed on a polyimide film by screen printing. A slurry in a water/alcohol mixed solvent was prepared using a catalyst powder having 30 wt. % of platinum fine particles borne on a carbon carrier and 30 wt. % of a perfluorocarbonsulfonic acid (“Nafion 117”, trade name; product of DuPont) electrolyte as a binder. By using the resulting slurry, a cathode porous membrane of about 10 μm thick was prepared on a polyimide film by screen printing.
The anode porous membrane and cathode porous membrane thus prepared were cut, respectively, into an anode electrode and a cathode electrode of 10 mm wide and 20 mm long. After the surface of the anode electrode was immersed with about 0.5 ml of a 5 wt. % solution of the sulfomethylated polyethersulfone obtained above in (3) in a-mixed solvent of 1-propanol, 2-propanol and methoxyethanol, the resulting anode electrode was bonded to the power generation portion of the sulfomethylated polyethersulfone electrolyte membrane prepared above in (4) and cut into a piece of 16 mm wide and 33 mm long. A load of about 1 kg was applied, followed by drying at 80° C. for 3 hours. Then, lo the surface of the cathode electrode was immersed with about 0.5 ml of a 5 wt. % alcohol/water solution (a 20:40:40 (weight ratio) mixed solvent of water, isopropanol and n-propanol; product of Fluka Chemika) of Nafion 117. The resulting cathode electrode was bonded to the electrolyte membrane so as to overlap the anode layer bonded thereto previously. A load of about 1 kg was applied, followed by drying at 80° C. for 3 hours to prepare MEA (2).
A slurry in a water/alcohol mixed solvent (a 20/40/40 (weight ratio) mixed solvent of water, isopropanol and n-alcohol) was prepared using a catalyst powder having 50 wt. % of a 1/1 (atomic ratio) platinum/ruthenium alloy fine particles dispersed and borne on a carbon catalyst and 30 wt. % perfluorocarbonsulfonic acid (“Nafion 117”, trade name; product of DuPont) electrolyte as a binder. By using the resulting slurry, an anode porous membrane of about 30 μm thick was formed on a polyimide film by screen printing. Another slurry in a water/alcohol mixed solvent was prepared using a catalyst powder having 30 wt. % of platinum fine particles borne on a carbon carrier and 30 wt. % perfluorocarbonsulfonic acid (“Nafion 117”, trade name; product of DuPont) electrolyte as a binder. By using the resulting slurry, a cathode porous membrane of about 10 μm thick was prepared on a polyimide film by screen printing. The anode porous membrane and cathode porous membrane thus prepared were cut, respectively, into an anode electrode and a cathode electrode of 10 mm wide and 20 mm long. After the surface of the anode electrode was immersed with about 0.5 ml of a 5 wt. % solution of Nafion 117 in an alcohol/water solvent (a 20/40/40 (weight ratio) mixed solvent of water, isopropanol and n-propanol; product of Fluka Chemika), the resulting anode electrode was bonded to the power generation portion of the sulfomethylated polyethersulfone electrolyte membrane prepared above in (4) and cut into a piece of 16 mm wide and 33 mm long. A load of about 1 kg was applied, followed by drying at 80° C. for 3 hours.
Then, the surface of the cathode electrode was immersed with about 0.5 ml of a 5 wt. % solution of Nafion 117 in an alcohol/water mixed solvent (a 20/40/40 (weight ratio) mixed solvent of water, isopropanol and n-propanol; product of Fluka Chemika). The resulting cathode electrode was bonded to the electrolyte membrane so as to overlap the anode layer bonded thereto previously. A load of about 1 kg was applied, followed by drying at 80° C. for 3 hours to prepare MEA (3).
(5) Preparation of a Diffusion Layer
A water based dispersion (“Dispersion D-1”, trade name; product of Daikin Industry) of a water repellent, more specifically, polytetrafluoroethylene (PTFE) fine particles was added to carbon powder so as to give its weight of 40 wt. % after baking. The resulting mixture was kneaded. The paste thus obtained was applied to one side of a carbon cloth of about 350 μm thick and having a porosity of 87%, followed by drying at room temperature and then baking at 270° C. for 3 hours, whereby a carbon sheet was obtained. The amount of PTFE was adjusted to fall within a range of from 5 to 20 wt. % relative to that of the carbon cloth. The sheet thus obtained was cut into a similar size to that of the electrode of the MEA, whereby a cathode diffusion layer was obtained.
As an anode diffusion layer of (A) of Example 1, a carbon cloth not subjected to treatment and having a thickness of about 350 μm and a porosity of 87% was used. The carbon cloth of about 350 μm thick and having a porosity of 87% was immersed in fuming sulfuric acid (concentration: 60%) and kept at 60° C. for 2 days under a nitrogen gas stream. The temperature of the flask was cooled to room temperature. The fuming sulfuric acid was removed and the carbon cloth was washed sufficiently with distilled water until the distilled water became neutral. The resulting carbon cloth was then immersed in methanol, followed by drying. As a result of infrared absorption spectrum of the carbon cloth, absorption based on —OSO3H group was observed at 1225 cm−1 and 1413 cm−1. In addition, absorption based on —OH group was observed at 1049 cm−1. This suggests that −OSO3H group and —OH group have been introduced into the surface of the carbon cloth and it is hydrophilic judging from the contact angle of it smaller than the contact angle 81° between a carbon cloth not treated with fuming sulfuric acid and an aqueous methanol solution. In addition, it has excellent conductivity. The carbon cloth thus obtained was cut into an equal size to that of the above-described MEA and used as a cathode diffusion layer (B) of Example 1 subjected to hydrophilization treatment (1).
To 297 parts by weight of tetrahydrofuran was added 1 part by weight of polyethylene glycol having a molecular weight of 20,000. The resulting mixture was stirred under heating to 50° C. to prepare the corresponding solution. To the resulting solution was added 2 parts by weight of “Sila-Ace S330” (trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to prepare a hydrophilic film forming coating. In the resulting coating, a carbon cloth having a thickness of about 350 μm and having a porosity of 87% and subjected to oxygen plasma treatment was immersed and the resulting cloth was heat treated at 100° C. for 20 minutes. The carbon cloth was cut into an equal size to that of the electrode of the above-described MEA and used as a cathode layer (C) of Example 1 subjected to hydrophilization treatment (2).
Carbon paper having a thickness of about 150 μm and porosity of 87% was immersed in fuming sulfuric acid (concentration: 60%) and kept at 60° C. for 2 days under a nitrogen gas stream. The temperature of the flask was then cooled to room temperature. The fuming sulfuric acid was removed and the carbon paper was washed completely with distilled water until the water became neutral. The resulting carbon paper was then immersed in methanol, followed by drying. As a result of infrared absorption spectrum of the carbon paper, absorption based on —OSO3H group was observed at 1225 cm−1 and 1413 cm−1. In addition, absorption based on —OH group was observed at 1049 cm−1. This suggests that —OSO3H group and —OH group have been introduced into the surface of the carbon paper and it is hydrophilic judging from the contact angle of it smaller than the contact angle 81° between carbon paper not treated with fuming sulfuric acid and an aqueous methanol solution. In addition, it has excellent conductivity. The carbon paper thus obtained was cut into a similar size to that of the electrode of above-described MEA and used as a cathode diffusion layer (D) of Example 1 subjected to hydrophilization treatment (3).
To 297 parts by weight of tetrahydrofuran was added 1 part by weight of polyethylene glycol having a molecular weight of 20,000. The resulting mixture was stirred under heating to 500° C. to prepare the corresponding solution. To the resulting solution was added 2 parts by weight of “Sila-Ace S330” (trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to prepare a hydrophilic film forming coating. In the resulting coating, carbon paper having a thickness of about 150 μm and a porosity of 87% and subjected to oxygen plasma treatment was immersed for about 5 minutes. The resulting carbon paper was taken out from the coating and heat treated at 100° C. for 20 minutes. The resulting hydrophilized carbon paper was cut into an equal size to that of the electrode of the above-described MEA and used as a cathode layer (E) of Example 1 subjected to hydrophilization treatment (4).
(6) Measurement of Contact Angle
Anode diffusion layers subjected to water repellent treatment, no treatment, hydrophilization treatment (1), hydrophilization treatment (2), hydrophilization treatment (3) and hydrophilization treatment (4) were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The samples were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as illustrated in Table 1, the anode diffusion layers of Comparative Example subjected to water repellent treatment each had a contact angle of 79° or greater, exhibiting water repellency. The anode diffusion layers subjected to hydrophilization treatment, on the other hand, had a contact angle of 20° or less in the initial stage and exhibited hydrophilic property, but the hydrophilic property reduced gradually.
(7) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage of Fuel Cell (DMFC) Power Source System
A fuel cell power source system as illustrated in
Anode diffusion layers dipped in a 20 wt. % aqueous methanol solution of 60° C. for 2 days, 15 days and 60 days were used to manufacture a fuel cell power source system of
(1) Preparation of Electrolyte Membrane Electrode Assembly (MEA)
An electrolyte membrane electrode assembly (MEA) was prepared in a similar manner to Example 1 except that an anode electrode hydrolyzed by dissolving, in a slurry of 50 wt. % of 1/1 (atomic ratio) platinum/ruthenium alloy fine particles dispersed and borne on a carbon carrier and the 30 wt. % sulfomethylated polyethersulfone obtained above in (3) in a mixed solvent of 1-propanol, 2-propanol and methoxyethanol, polyoxyalkylene glycol and 3-heptanol to give them 0.01 wt. % and 0.05 wt. %, respectively.
(2) Preparation of Anode Diffusion Layer (0)
An untreated carbon cloth having a thickness of about 350 μm and porosity of 87% was dipped in ethyl alcohol in which polyoxyalkylene glycol and 3-heptanol had been dissolved to give their concentrations of 0.01 wt. % and 0.05 wt. %, respectively, followed by drying. The resulting cloth was cut into an equal size of the electrode of the above-described MEA to prepare a cathode diffusion layer (D) of Comparative Example 1 subjected to hydrophilization treatment (0).
(3) Measurement of Contact Angle, Foam Discharging Performance, Internal Pressure and Output Voltage
Anode diffusion layers subjected to water repellent treatment and hydrophilization treatment (0) were each immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The samples were taken out after, 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as shown in Comparative Example in Table 1, the anode diffusion layer subjected to water repellent treatment had a contact angle of 79° or greater, exhibiting water repellency. The anode diffusion layer subjected to hydrophilization treatment, on the other hand, had a contact angle of 20° or less in the initial stage and exhibited hydrophilic property. Immersion in a 20 wt. % aqueous methanol solution only for 2 days however caused a drastic increase in the contact angle, suggesting weakening of hydrophilic property.
A fuel cell power source system as illustrated in
Examples (A) to (E) and Comparative Examples (A) to (D) in Tables 1 and 2 have revealed that an anode diffusion layer subjected to hydrophilization treatment shows good foam discharging performance for long hours, does not show any increase in internal pressure which permits smooth supply of fuel, and therefore enables power generation. In particular, hydrophilization treatment including reaction with a diffusion layer is superior.
(B): water repellent treatment *1: combination of an electrode treated with a defoaming agent and an anode diffusion layer subjected to water repellent treatment
(C) Water repellent treatment *2: combination of an electrode containing a carbonate ion trapping agent and an anode diffusion layer subjected to water repellent treatment
(D) Treatment with defoaming agent *3: electrode and anode diffusion layer both treated with a defoaming agent
(1) Manufacture of Anode Endplate and Current Collector
Anode endplates and current collectors were manufactured by changing the short side/long side ratio of slits 122, 122a, 122b and 122c serving as transmission holes of fuel and carbon dioxide gas to 0.2, 0.36, 0.5, 0.8 and 1.0. The anode endplate and current collector were bonded and integrated by an epoxy resin. In addition, anode endplates and current collectors were manufactured by changing angles between the surface of the anode electrode and slits 122, 122a, 122b and 122c extending from the electrode toward the fuel tank to 90°, 85°, 80° and 70°, while fixing the short side/long side ratio to 0.36. The anode endplates and current collectors were bonded and integrated by an epoxy resin.
(2) Measurement of Contact Angle
The anode endplates integrated with the current collectors manufactured above in (1) were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The samples were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, any of these anode endplates integrated with the current collectors showed a contact angle of 70° or greater as shown in Examples in Tables 3 and 4.
A short side/long side ratio: A short side/long side ratio of slits (fuel transmission holes) 122, 122a, 122b, 122c
Angle of inclination: Angle of inclinations of slits (fuel transmission holes) 122, 122a, 122b and 122c extending from the anode electrode side to the outside
(3) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage of Fuel Cell (DMFC) Power Source System
A fuel cell power source system of
In the initial stage, all the systems except that with a slit hole having a short side/long side ratio of 1.0 showed good foam discharging performance, did not show an increase in internal pressure and had an output voltage of 1.4V or greater. The system with a slit hole having a short side/long side ratio of 1.0 was inferior in foam discharging performance, and showed an increase in internal pressure and unstable output voltage. The short side/long side ratio is preferably not 1.0, meaning that the vertical length differs with the horizontal length. From the standpoint of foam discharging performance, the short side/long side ratio of the slit hole of the anode endplate integrated with current collector is preferably other than 1.0. The short side/long side ratio is desirably adjusted to from 0.2 to 0.8, more preferably from 0.3 to 0.6.
With regards to the angle between the surface of the anode electrode and the slits 122, 122a, 122b and 122c of the anode endplate integrated with current collector extending from the electrode side toward the fuel tank, when it is 90°, the system showed poor foam discharging performance, high internal pressure and unstable output voltage. When the inclination angle of the slit of the anode endplate integrated with current colleting plate is set at 85°, 80° or 70° so as to make it wider from the anode diffusion layer side toward the air layer side, the foam discharging performance is improved, an increase in internal pressure becomes small and output voltage becomes stable.
The above-described findings suggest that by adjusting the short side/long side ratio of the slit of the anode endplate integrated with current collector to other than 1 and inclining the slit of the anode endplate integrated with current collector to be wider from the anode diffusion layer side to the air layer side, a gas can be discharged from the anode endplate integrated with current collector promptly, an increase in internal pressure can be suppressed and a high output voltage can be maintained stably for a long period of time.
Example 3Anode endplates integrated with current collector subjected to UV/ozone treatment for 20 minutes, excimer laser treatment for 5 minutes, 10 minutes, 20 minutes or 30 minutes, or oxygen plasma treatment for 10 seconds were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel. The vessel was then put in an SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The anode endplates integrated with current collector were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. Results are shown in Tables 5 and 6. The anode endplates integrated with current collector subjected to UV/ozone treatment or oxygen plasma treatment had a contact angle of from 17 to 19°, while the anode endplates integrated with current collector subjected to excimer laser treatment had a contact angle of from 45 to 47°. Immersion in a 20 wt. % aqueous methanol solution of 60° C. gradually increases the contact angle of each of the anode endplates integrated with current collector subjected to UV/ozone treatment, oxygen plasma treatment or excimer laser treatment. This phenomenon is presumed to occur because when they were immersed in a 20 wt. % aqueous methanol solution for long hours, transfer of the hydrophilic group on the surface of the anode endplate such as carbonyl, carboxyl or hydroxyl group to the inside of the endplate occurs, leading to a decrease in hydrophilic property on the surface of the anode endplate. When the influence of exposure time of the anode endplates integrated with current collector subjected to excimer laser treatment was investigated, the longer the exposure time, the smaller an increase in the contact angle even if the plate was immersed in a 20 wt. % aqueous methanol solution of 60° C. for long hours. This phenomenon is presumed to occur because even if a hydrophilic group such as carbonyl, carboxyl or hydroxyl group on the surface of the anode endplate transfers inside of the endplate, a hydrophilic group such as carbonyl, carboxyl or hydroxyl group has already been introduced into a deeper portion of the anode endplate as the exposure time is longer and it is not lost from the surface.
A fuel cell power source system of
Compared with the anode endplate integrated with current collector subjected to no treatment, the above-described ones each showed good foam discharging performance, did not show an increase in internal pressure and exhibited stable output. Immersion of the anode endplate integrated with current collector subjected to UV/ozone treatment, oxygen plasma treatment or excimer laser treatment in a 20 wt. % aqueous methanol solution of 60° C. caused gradual deterioration in the foam discharging performance, increase in the pressure in the DMFC and unstable output voltage. This phenomenon is presumed to occur because immersion in a 20 wt. % aqueous methanol solution of 60° C. causes transfer of the hydrophilic group such as carbonyl group, carboxyl group or hydroxyl group from the surface of the endplate to the inside of the endplate, which causes reduction in hydrophilicity on the surface of the anode endplate.
When the exposure time is longer, the anode endplate integrated with current collector shows better foam discharging performance, does not show an increase in internal pressure and has more stable output voltage even if it is immersed in a 20 wt. % aqueous methanol solution of 60° C. This phenomenon is presumed to occur because even if a hydrophilic group such as carbonyl, carboxyl or hydroxyl group on the surface of the anode endplate transfers inside of the endplate, a hydrophilic group such as carbonyl, carboxyl or hydroxyl group has already been introduced into a deeper portion of the anode endplate as the exposure time is longer and it is not lost from the surface.
As can be understood from Tables 5 and 6, compared with the anode endplate integrated with current collector subjected to no treatment, the anode endplate integrated with current collector having a hydrophilic group such as carbonyl, carboxyl or hydroxyl group introduced therein by hydrophilization treatment with UV/ozone, excimer laser, oxygen plasma, corona discharge, electron beam or radiation can promptly discharge a gas such as carbon dioxide gas generated at the anode, prevents an increase an internal pressure and produces high output voltage stably.
An anode endplate integrated with current collector was sandblasted with alumina having a grain size of each of #1200, #800, #600, #320, #150 and #60 under the conditions of gun diameter of 9 mm, gun distance of 100 mm and gun moving speed of 50 mm/sec at an injection pressure of each of 0.2 MPa, 0.3 MPa and 0.4 MPa.
The above-described sandblasted anode endplates integrated with current collector were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The anode endplates integrated with current collector were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. Each contact angle of the plates with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as shown in Example in Table 7, it falls within a range of from 70° to 76° and no change was recognized even by immersion in a 20 wt. % aqueous methanol solution of 60° C.
A fuel cell power source system of
(1) Preparation of Hydrophilic Film Forming Coating
To 297 parts by weight of tetrahydrofuran (THF) was added 1 part by weight of polyethylene glycol having an average molecular weight of 6,000. The resulting mixture was stirred under heating to 50° C. to prepare the corresponding solution. To the resulting solution were added 2 parts by weight of “Sila-Ace S310”, “S320”, “S330”, “S360”, “MS3201” and “MS3301” (each, trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to yield hydrophilic film forming coatings (A), (B), (C), (D), (E) and (F), respectively. In addition, 1 part by weight of polyethylene glycol having an average molecular weight of 2,000,000 was added to 297 parts by weight of tetrahydrofuran (THF). The resulting mixture was stirred under heating to 50° C. to prepare the corresponding solution. To the resulting solution were added 2 parts by weight of “Sila-Ace S310”, “S320”, and “MS3301” (each, trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to yield hydrophilic film forming coatings (G), (H) and (I), respectively.
(3) Chemical Hydrophilic Treatment of Anode Endplate Integrated with Current Collector
The current collector portions of the anode endplates integrated with current collector were masked with a masking tape, followed by oxygen/plasma treatment for 10 seconds. Then, the resulting plates were immersed in the above-described hydrophilic film forming coatings (A) to (I), respectively, for 30 seconds. After taken out from the coatings, they were heated to 110° C. for about 30 seconds to form a hydrophilic film on the surface of the anode endplates.
(4) Measurement of Contact Angle
The anode endplates integrated with current collector manufactured in (2) were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The resulting anode endplates integrated with current collector were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as illustrated in Table 5, the plates had a contact angle of 20° or less, exhibited high hydrophilic property and were stable even if they were immersed in a 20 wt. % aqueous methanol solution of 60° C. for long hours.
(5) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage of Fuel Cell (DMFC) Power Source System
Fuel cell power source systems as illustrated in
The fuel cell power source system using the anode endplate integrated with current collector showed good foam discharging performance, no increase in internal pressure and stable output voltage of 1.7V or greater in the initial stage and 60 days after immersion in a 20 wt. % aqueous methanol solution of 60° C.
The above-described finding suggests that application of a reactive hydrophilic coating to the surface of an anode endplate integrated with current collector enables prompt discharge of a gas such as carbon dioxide gas generated at the anode electrode portion, prevention of an increase in internal pressure and supply of a high output voltage stably for a prolonged period of time.
Example 6(1) Preparation of Hydrophilic Film Forming Coating
To 297 parts by weight of tetrahydrofuran (THF) was added 1 part by weight of polyethylene glycol having an average molecular weight of 8,000. The resulting mixture was stirred under heating to 50° C. to prepare the corresponding solution. To the resulting solution were added 2 parts by weight of “Sila-Ace S310”, “S320”, “S330”, “S360”, “MS3201” and “MS3301” (each, trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to yield hydrophilic film forming coatings (A), (B), (C), (D), (E) and (F), respectively. In addition, 1 part by weight of polyethylene glycol having an average molecular weight of 1,000,000 was added to 297 parts by weight of tetrahydrofuran (THF). The resulting mixture was stirred under heating to 50° C. to prepare the corresponding solution. To the resulting solution were added 2 parts by weight of “Sila-Ace S310”, “S320”, and “MS3301” (each, trade name; product of Chisso Corporation) having both an amino group and an alkoxysilane residue, followed by stirring to yield hydrophilic film forming coatings (G), (H) and (I), respectively.
(2) Chemical Hydrophilic Treatment of Anode Endplate Integrated with Current Collector
The current collector portions of the anode endplates integrated with current collector were masked with a masking tape and subjected to UV/ozone treatment by exposing them to a low pressure mercury lamp under conditions of lamp intensity of 55 mW and exposure time of 1 minute. Then, the resulting plates were immersed in the above-described hydrophilic film forming coatings (A) to (I), respectively, for 30 seconds. After they were taken out from the coatings, they were heated at 110° C. for about 30 seconds to form a hydrophilic film on the surface of the anode endplate.
(3) Measurement of Contact Angle
The anode endplates integrated with current collector manufactured in (2) were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The anode endplates integrated with current collector were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as illustrated in Tables 13 and 14, the plates had a contact angle of 20° or less, exhibited high hydrophilicity and was stable even if they were immersed in a 20 wt. % aqueous methanol solution of 60° C. for long hours.
(4) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage of Fuel Cell (DMFC) Power Source System
A fuel cell power source system as illustrated in
The fuel cell power source system using the anode endplate integrated with current collector showed good foam discharging performance and did not, show an increase in internal pressure and had an output voltage of 1.7V or greater both in the initial stage and 60 days after immersion in a 20 wt. % aqueous methanol solution.
The above-described finding suggests that application of a reactive hydrophilic coating onto the surface of an anode endplate integrated with current collector enables prompt discharge of a gas such as carbon dioxide gas generated at an anode electrode portion, prevention of an increase in internal pressure and stable supply of high output voltage for a long period of time.
Example 7(1) Preparation of Hydrophilic Film Forming Coating
A 0.01 wt. % ethanol solution of polyoxyalkylene glycol, a 0.05 wt. % ethanol solution of polyoxyethylene alkylphenyl ether, a 0.05 wt. % ethanol solution of 3-heptyl cellosolve phenol, a 0.05 wt. % ethanol solution of diethylene glycol monooleate, a 0.1 wt. % ethanol solution of ethylene glycol distearate, a 0.05 wt. % ethanol solution of γ-glycidoxypropyltrimethoxysilane, a 0.05 wt. % ethanol solution of epoxyaminosilane, a 0.05 wt. % ethanol solution of aminoalkoxysilane, and a 0.005 wt. % ethanol solution of tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate were prepared as hydrophilic film forming coatings (A) to (I), respectively.
(2) Chemical Hydrophilic Treatment of Anode Endplate Integrated with Current Collector
The current collector portions of the anode endplates integrated with current collector were masked with a masking tape and they were subjected to corona discharge treatment. Then, the resulting plates were immersed in the above-described hydrophilic film forming coatings (A) to (I), respectively, for 30 seconds. After they were taken out from the coatings, they were heated to 110° C. for about 30 seconds to form hydrophilic films on the surface of the anode endplates.
(3) Measurement of Contact Angle
The anode endplates integrated with current collector manufactured in (1) were immersed in a 20 wt. % aqueous methanol solution contained in a Teflon (trade mark) vessel and the vessel was put in a SUS pressure container. The pressure container was allowed to stand in a thermostat bath of 60° C. The samples were taken out after 2 days, 15 days and 60 days, respectively and wiped gently with “Kimwipe”. The contact angle with water was then measured using a contact angle meter “CA-D” (trade name) manufactured by Kyowa Interface Science. As a result, as illustrated in Tables 15 and 16, any of the plates had a contact angle of 20° or less and exhibited high hydrophilic property in the initial stage. Immersion in a 20 wt. % aqueous methanol solution of 60° C. for long hours gradually increased the contact angles of the anode endplates (A) to (E). Fuel power source systems having, incorporated therein, the anode endplates (F) to (I) to which hydrophilic agents reactive with the surface of the anode endplates were applied had a contact angle of 20° or less, thus showing super hydrophilic property even after immersion in a 20 wt. % aqueous methanol solution of 60° C. for long hours.
(4) Measurement of Foam Discharging Performance, Internal Pressure and Output Voltage of Fuel Cell (DMFC) Power Source System
A fuel cell power source system as illustrated in
The fuel cell power source system using the anode endplate integrated with current collector in the initial stage showed good foam discharging performance, did not show an increase in internal pressure and exhibited stable output voltage of 1.7V or greater. It has been found that the fuel cell power source systems having the anode endplates (A) to (E) incorporated therein tended to become hydrophobic gradually, have deteriorated foam discharging performance, have increased internal pressure and have less uniform output voltage when immersed in a 20 wt. % aqueous methanol solution of 60° C. The fuel cell power source systems having incorporated therein the anode endplates (F) to (I) treated with a reactive hydrophilic film forming coating showed good foam discharging performance, did not show an increase in internal pressure and had stable output voltage of 1.7V or greater even when immersed in a 20 wt. % aqueous methanol solution of 60° C.
The above-described finding suggests that application of a hydrophilic coating (especially, reactive) onto the surface of an anode endplate integrated with current collector enables prompt discharge of a gas such as carbon dioxide gas generated at an anode electrode portion, prevention of an increase in internal pressure and stable supply of high output voltage for a long period of time.
As is apparent from Examples so far described, in a fuel cell which comprises a membrane electrode assembly for producing power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for transmitting fuel and transferring electrons produced by oxidation to the outside of the anode electrode of the membrane electrode assembly, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector and an anode endplate for transferring electrons generated by the oxidation outside the anode diffusion layer, and a cathode current collector and cathode endplate for transferring electrons to be used for the reduction outside the cathode diffusion layer, the following methods are employed either singly or in combination of two or more:
(i) to make the anode diffusion layer non-water repellent.
(ii) to make the anode diffusion layer hydrophilic.
(iii) to adjust a short side/long side ratio of the slits of the anode current collectors and anode end plates to from 0.2 to 0.95.
(iv) to incline the slits of the anode endplate and current collector so that they become wider from the anode diffusion layer side toward the air layer side.
(v) to roughen the surface of an anode endplate by physical means such as sandblast.
(vi) to hydrophilize an anode endplate, especially with a reactive hydrophilizing agent.
By the above-described methods, it is possible to prevent a gas such as carbon dioxide or carbon monoxide generated at an anode from adsorbing to an anode diffusion layer or endplate, carry out discharge of the gas from the anode diffusion layer smoothly to prevent an increase in internal pressure and supply a high output voltage stably for a prolonged period of time.
Use of the fuel cell power source system of the present invention as a battery charger attached to personal digital assistance such as mobile phone having a built-in secondary battery, mobile personal computer, mobile audio, digital camera or visual devices or use of it as a built-in power source directly without using a second battery makes it possible to prolong the operation time of these electronic devices and use them continuously by supply of fuel.
Claims
1. A fuel cell having a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for allowing fuel to pass therethrough toward the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode-electrode, an anode current collector and anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and a cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer, wherein the anode endplate or anode current collecting layer is hydrophilic or the end plate on the anode side has a constitution promoting discharge of a gas generated by the reaction.
2. A fuel cell according to claim 1, wherein the anode diffusion layer has been subjected to hydrophilization treatment.
3. A fuel cell according to claim 1, wherein the anode current collector has slits, each having a short side/long side ratio of from 0.5 to 0.92.
4. A fuel cell according to claim 1, wherein the slits of the anode endplate are inclined so as to widen their width from the electrode side toward the fuel chamber side.
5. A fuel cell according to claim 1, wherein the anode endplate has been subjected to chemical or physical hydrophilization treatment.
6. A fuel cell according to claim 5, wherein the chemical treatment means treatment with a hydrophilizing agent.
7. A fuel cell according to claim 5, wherein the chemical treatment means treatment with UV/ozone, excimer laser or oxygen lo plasma.
8. A fuel cell according to claim 7 wherein the chemical treatment means treatment with UV/ozone, excimer laser or oxygen plasma, then with a hydrophilizing agent.
9. A fuel cell according to claim 1, wherein the anode endplate has been physically roughened.
10. A fuel cell according to claim 9, wherein the physical roughening treatment is sandblasting.
11. A fuel cell power source system comprising a fuel cell as claimed in claim 1 and a power source control portion and a DC-DC converter attached thereto.
12. An electronic device comprising a fuel cell power source system as claimed in claim 11 attached thereto.
13. An electronic device according to claim 11, which is any one of a personal digital assistance, notebook mobile personal computer, mobile phone and camcorder.
14. An electronic device according to claim 11, which is an outdoor portable power source.
15. A fuel cell comprising a membrane electrode assembly for generating power by oxidizing methanol fuel at an anode electrode and reducing oxygen in the air at a cathode electrode, an anode diffusion layer located on a side opposite to the cathode electrode of the membrane electrode assembly and serving to allow fuel to pass through the anode diffusion layer and transfer electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector which is brought into contact with the anode diffusion layer directly or via another member and serves to transfer electrons generated by the oxidation, an anode endplate which is brought into electrical contact with the anode current collector, a cathode current collector which is brought into contact with the cathode diffusion layer directly or via another member and serves to transfer electrons to be used for the reduction, and a cathode endplate which is brought into electrical contact with the cathode current collector, wherein the anode endplate is hydrophilic and the cathode current collector side is constituted to come into contact with the air.
16. A fuel cell comprising a membrane electrode assembly having an electrolyte membrane and an electrode, a cathode diffusion layer and an anode diffusion layer located on both sides of the membrane electrode assembly, respectively, a cathode current collector and an anode current collector located outside of the diffusion layers, and endplates which surround the cathode current collector and anode current collector and have slits, respectively, wherein the cathode diffusion layer is brought into contact with the air via slits on the side of the cathode current collector, methanol fuel is brought into contact with the anode diffusion layer via the slits on the side of the anode current collector, and the anode endplate surrounding the anode current collector therewith is, in a region in contact with the methanol fuel, hydrophilic.
17. A fuel cell comprising a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for allowing fuel to pass therethrough to the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector and an anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer, wherein the anode diffusion layer has been hydrophilized.
18. A fuel cell comprising a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for allowing fuel to pass therethrough to the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector and an anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer, wherein the anode current collector has slits, each having a short side/long side ratio of from 0.5 to 0.92.
19. A fuel cell comprising a membrane electrode assembly for generating power by oxidizing fuel at an anode electrode and reducing oxygen at a cathode electrode, an anode diffusion layer for allowing fuel to pass therethrough to the outside of the anode electrode of the membrane electrode assembly and transferring electrons generated by the oxidation, a cathode diffusion layer for removing water thus generated and transferring electrons to be used for the reduction to the outside of the cathode electrode, an anode current collector and an anode endplate for transferring electrons generated by the oxidation to the outside of the anode diffusion layer, and a cathode current collector and cathode endplate for transferring electrons to be used for the reduction to the outside of the cathode diffusion layer, wherein the slits of the anode endplate are each inclined to become wider from the electrode side toward the fuel chamber side.
Type: Application
Filed: Feb 17, 2006
Publication Date: Feb 15, 2007
Patent Grant number: 7803496
Inventors: Toru Koyama (Hitachi), Osamu Kubota (Hitachi), Hiroshi Sasaki (Mito), Kenichi Souma (Mito)
Application Number: 11/356,101
International Classification: H01M 4/94 (20070101); H01M 8/02 (20070101);
